WO2019005710A1 - Procédé d'hydrosilylation d'alcoxysilanes aliphatiquement insaturés et d'oligomères d'organosiloxane à terminaison hydrogène pour préparer des polymères à terminaison alcoxysilyle utiles pour fonctionnaliser des polyorganosiloxanes à l'aide d'un catalyseur au rhodium - Google Patents

Procédé d'hydrosilylation d'alcoxysilanes aliphatiquement insaturés et d'oligomères d'organosiloxane à terminaison hydrogène pour préparer des polymères à terminaison alcoxysilyle utiles pour fonctionnaliser des polyorganosiloxanes à l'aide d'un catalyseur au rhodium Download PDF

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WO2019005710A1
WO2019005710A1 PCT/US2018/039377 US2018039377W WO2019005710A1 WO 2019005710 A1 WO2019005710 A1 WO 2019005710A1 US 2018039377 W US2018039377 W US 2018039377W WO 2019005710 A1 WO2019005710 A1 WO 2019005710A1
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hydrocarbon group
alkoxy
independently
formula
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PCT/US2018/039377
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Matthew OLSEN
John Gohndrone
Xiaoyuan Zhou
William Johnson
Christine Marchand
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Dow Silicones Corporation
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Priority to JP2019567993A priority Critical patent/JP7189157B2/ja
Priority to US16/617,679 priority patent/US11098163B2/en
Priority to CN201880038458.2A priority patent/CN110770280B/zh
Priority to EP18743152.3A priority patent/EP3645606A1/fr
Publication of WO2019005710A1 publication Critical patent/WO2019005710A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • vinyltrimethoxysilane with 1 ,1 ,3,3-tetramethyldisiloxane using a platinum catalyst yields a mixture including the a-adduct branched isomer and ⁇ -adduct linear isomer as reaction products.
  • a method for selectively preparing a product comprising an alkoxy-functional organohydrogensiloxane oligomer comprises:
  • each R 1 is independently a monovalent hydrocarbon group of 1 to 18 carbon or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms;
  • each R 2 is independently an aliphatically unsaturated monovalent hydrocarbon group of 2 to 18 carbon atoms, each
  • R3 is independently a monovalent hydrocarbon group of 1 to 18 carbon atoms, subscript c is 0 or 1 ;
  • step 2 isolating the alkoxy-functional organohydrogensiloxane oligomer prepared in step 1 ).
  • the alkoxy-functional organohydrogensiloxane oligomer has unit formula:
  • the alkoxy-functional organohydrogensiloxane oligomer is useful in a method for preparing a poly-alkoxy functional polyorganosiloxane.
  • the method for preparing the poly-alkoxy functional polyorganosiloxane comprises:
  • the method for selectively preparing a product comprising an alkoxy-functional organohydrogensiloxane oligomer comprises:
  • each R 1 is independently a monovalent hydrocarbon group of 1 to 18 carbon or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms;
  • each R 2 is independently an aliphatically unsaturated monovalent hydrocarbon group of 2 to 18 carbon atoms
  • each R ⁇ is independently a monovalent hydrocarbon group of 1 to 18 carbon atoms
  • subscript c is 0 or 1 ;
  • Ingredient (A) useful in the method described above is a
  • each R 1 is independently a monovalent hydrocarbon group of 1 to 18 carbon or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms.
  • monovalent hydrocarbon groups for R 1 have 1 to 12
  • Suitable monovalent hydrocarbon groups for R 1 include, but are not limited to, an alkyl group of 1 to 6 carbon atoms and an aryl group of 6 to 10 carbon atoms.
  • Suitable alkyl groups for R 1 are exemplified by, but not limited to, methyl, ethyl, propyl ⁇ e.g., iso-propyl and/or n-propyl), butyl ⁇ e.g., isobutyl, n-butyl, tert-butyl, and/or sec- butyl), pentyl ⁇ e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, as well as branched saturated hydrocarbon groups of 6 carbon atoms.
  • Suitable aryl groups for R 1 are exemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl.
  • Suitable monovalent halogenated hydrocarbon groups for R 1 include, but are not limited to, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms.
  • Suitable halogenated alkyl groups for R 1 are exemplified by, but not limited to, the alkyl groups described above where one or more hydrogen atoms is replaced with a halogen atom, such as F or CI.
  • Suitable halogenated aryl groups for R 1 are exemplified by, but not limited to, the aryl groups described above where one or more hydrogen atoms is replaced with a halogen atom, such as F or CI.
  • a halogen atom such as F or CI.
  • chlorobenzyl and fluorobenzyl are suitable halogenated aryl groups.
  • each R 1 is independently methyl, ethyl or propyl. Each instance of R 1 may be the same or different.
  • each R 1 is a methyl group.
  • suitable hydridosilanes include trimethylsilane and trimethoxysilane.
  • ingredient (A) is an ⁇ , ⁇ -hydrogen terminated organohydrogensiloxane oligomer of formula (IV):
  • each R 1 is independently an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 10 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms; and subscript a is an integer up to 20.
  • subscript a is 0 to 20
  • alternatively subscript a is 0 to 10
  • alternatively subscript a is 0 to 5
  • alternatively subscript a is 0 or 1.
  • subscript a may be 2 to 10; alternatively subscript a is 2 to 5.
  • organohydrogensiloxane oligomers examples include 1 ,1 ,3,3,5,5-hexamethyltrisiloxane, 1 ,1 ,3,3- tetramethyldisiloxane, 1 ,1 ,3,3,5,5-hexaethyltrisiloxane, and 1 ,1 ,3,3-tetraethyldisiloxane.
  • ingredient (A) may be 1 ,1 ,3,3- tetramethyldisiloxane.
  • the product comprises an alkoxy-functional organohydrogensiloxane oligomer produced of formula (V):
  • D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that > 90 mol% of D are linear divalent hydrocarbon groups.
  • ingredient (A) the organohydrogensiloxane oligomer has unit formula (VI): (HR 1 2SiOi/2)3(R 1 2SiC>2/2)q(R 1 SiC>3/2), where subscript q is 0 to 3.
  • the polyorganohydrogensiloxane oligomer of this unit formula may have formula (VII): H
  • organohydrogensiloxane oligomers include siloxanes of formula
  • the product comprises an alkoxy- functional organohydrogensiloxane oligomer of formula (VIII) where formula (VIII) is:
  • each D is independently a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that > 90 mol% of D are linear divalent hydrocarbon groups.
  • organohydrogensiloxane oligomer may have unit formula (IX):
  • the organohydrogensiloxane oligomer may have formula (X):
  • the product comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (XI), formula (XII), or a combination thereof, where formula (XI) is (O 1 )(3-c) R 1 H R ' R '
  • ingredient (A) the organohydrogensiloxane oligomer is cyclic.
  • the cyclic organohydrogensiloxane oligomer may have unit formula
  • Ingredient (B) useful in the method described above is an aliphatically unsaturated alkoxysilane of formula (XV): R 1 where each R 1 is
  • each R 2 is independently an aliphatically unsaturated hydrocarbon group, each R ⁇ is independently a monovalent hydrocarbon group, subscript d is 0 or 1 .
  • the aliphatically unsaturated hydrocarbon group for R 2 may be an alkenyl group or an alkynyl group. Suitable alkenyl groups include vinyl, allyl, propenyl, butenyl and hexenyl; alternatively vinyl, allyl or hexenyl; and alternatively vinyl.
  • the monovalent hydrocarbon group for R3 may be a monovalent hydrocarbon group as described above for R 1 .
  • Ingredient (B) may comprise an aliphatically unsaturated alkoxysilane exemplified by a dialkoxysilane, such as a dialkenyldialkoxysilane; a trialkoxysilane, such as an alkenyltrialkoxysilane; or a combination thereof.
  • a dialkoxysilane such as a dialkenyldialkoxysilane
  • a trialkoxysilane such as an alkenyltrialkoxysilane
  • suitable aliphatically unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, hexenyltrimethoxysilane,
  • Ingredient (A) and ingredient (B) are present in relative molar amounts of ingredient (A):ingredient (B) of 1 :1 to > 1 :1 , alternatively greater than or equal to 1 , i.e., (A):(B) ratio ⁇ 1 :1 .
  • (A):(B) ratio may range from 5:1 to 1 :1 , alternatively 2:1 to 1 :1 ; and alternatively 1 .5:1 to 1 :1 .
  • a molar excess of ingredient (A) relative to ingredient (B) may favorably affect yield in the product.
  • Ingredient (C) useful in the method and composition described herein is a chelated rhodium diphosphine complex.
  • the chelated rhodium diphosphine complex may have formula (C1 ): [R (R5 2 P) 2 RhR6] 2 , formula (C2): [R (R5 2 P) 2 Rh(R6)] R 7 , or a mixture thereof.
  • each R 4 is independently a divalent hydrocarbon group
  • each R ⁇ is independently a monovalent hydrocarbon group
  • each R 6 is independently a negatively charged ligand
  • each J is
  • the divalent hydrocarbon group for R 4 may be an alkane-diyl, such as an alkane-diyl group of 1 to 6 carbon atoms.
  • R 4 may be methane- diyl, ethane-1 ,2-diyl, or hexane-1 ,6-diyl; and alternatively R 4 may be ethane-1 ,2-diyl.
  • the monovalent hydrocarbon group for may be an alkyl group or an aryl group.
  • Suitable alkyl groups for are exemplified by, but not limited to, methyl, ethyl, propyl ⁇ e.g., iso-propyl and/or n-propyl), butyl ⁇ e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl ⁇ e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, as well as branched saturated hydrocarbon groups of 6 carbon atoms.
  • the alkyl group for R ⁇ may be methyl, ethyl or propyl.
  • Suitable aryl groups for R ⁇ are exemplified by, but not limited to, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • R ⁇ may be an ethyl group or a phenyl group.
  • Examples of negatively charged ligand suitable for R 6 include a halogen atom, an alkoxy ligand, an aryl ligand, and a heteroaryl ligand.
  • suitable halogen atoms include bromine (Br), chlorine (CI) and iodine (I).
  • the halogen atom may be CI.
  • alkoxy ligands include methoxy, ethoxy, and propoxy.
  • alkoxy ligand may be methoxy.
  • suitable aryl ligands include phenyl, benzyl, or indenyl.
  • R 7 is an anion.
  • the anion may be what is referred to by those skilled in the art as a 'weakly coordinating anion' or a 'non-coordinating anion', including perchlorate, trifluoromethylsulfonate, tetrafluoroborate, tetrakisphenylborate, tetrakis(pentafluorophenyl)borate, methyltris(pentafluorophenyl)borate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, hexafluoroantimonate, hexafluorophosphate,
  • X represents a donor ligand.
  • donor ligands are nitriles such as acetonitrile, cyclized or non-cyclized ethers such as tetrahydrofuran or diethylether, dimethylsulfoxide, olefins such as 1 ,2-cis-cyclooctene or 1 -octene or ethylene, dienes such as 1 ,5-cyclooctadiene or 2,5-norbornadiene or 1 ,5-hexadiene, ketones such as acetone, or alkynes such as acetylene or 1 ,2-diphenylacetylene.
  • Examples suitable catalysts for ingredient (C) include, but are not limited to [1 ,2-bis(diphenylphosphino)ethane]dichlorodirhodium and [1 ,2- bis(diethylphospino)ethane]dichlorodirhodium, and mixtures thereof.
  • the amount of ingredient (C) used in step (1 ) of the method described above depends on various factors including the specific organohydrogensiloxane oligomer selected for ingredient (A), the specific alkoxysilane selected for ingredient (B), and the temperature to which the mixture can be heated without boiling away the organohydrogensiloxane oligomer selected for ingredient (A).
  • the amount of ingredient (C) may be sufficient to provide a molar amount of rhodium metal of 1 parts per million (ppm) to 100 ppm, alternatively 5 ppm to 80 ppm, alternatively 5 ppm to 20 ppm based on combined weights of ingredients (A) and (B).
  • the method may optionally further comprise deactivation or removal of the catalyst. However, with appropriate catalyst loading, the step of deactivation or removal of the catalyst may be omitted.
  • the method described herein may be performed at 1 atmosphere of pressure or higher. Alternatively, the method may be performed at 1 atmosphere to 1 .5 atmosphere. Step 1 ) may be performed at 0°C to 150°C, alternatively 50°C to 150°C, alternatively 60°C to 150°C, and alternatively 50°C to 100°C.
  • the temperature for heating in step 1 ) depends on various factors including the pressure selected, however, heating may be performed at least 70°C to ensure the reaction proceeds quickly enough to be practical.
  • the upper limit for temperature during heating is not critical and depends on the ingredients selected, i.e., the upper limit should be such that the ingredients do not vaporize out of the reactor selected for performing the method. Alternatively, heating may be from 70°C to 150°C, alternatively 70°C to 100°C.
  • Step (1 ) of the method described above produces a product comprising an alkoxy-functional organohydrogensiloxane oligomer.
  • the alkoxy-functional organohydrogensiloxane oligomer The alkoxy-functional
  • organohydrogensiloxane oligomer has unit formula (XVI):
  • Subscripts e, g, and j are as described above in formula (I).
  • the method described herein provides the benefit that this alkoxy-functional organohydrogensiloxane oligomer is produced with high selectivity to the ⁇ -adduct compound, i.e., where D is linear, with either none or lower amounts of the corresponding a-adduct compound than existing methods using other catalysts.
  • the ingredients in step 1 ) of the method described above form a mixture, which may be homogeneous or heterogeneous.
  • One or more additional ingredients, i.e., in addition to ingredients (A), (B), and (C) described above, may optionally be used in the method and composition described herein.
  • the additional ingredient, when present, may be (D) a solvent.
  • Ingredient (D) is a solvent that may be added to the mixture used in step 1 ) of the method described herein.
  • One or more of ingredients (A), (B), and/or (C) may be provided in a solvent.
  • the ingredient (C) may be dissolved in a solvent that is added to the mixture in step 1 ).
  • the solvent may facilitate contacting of reactants and catalyst, flow of the mixture and/or introduction of certain ingredients, such as the catalyst.
  • Solvents used herein are those that help fluidize the ingredients of the mixture but essentially do not react with any of these ingredients. Solvents may be selected based on solubility the ingredients in the mixture and volatility. The solubility refers to the solvent being sufficient to dissolve ingredients of the mixture.
  • Volatility refers to vapor pressure of the solvent. If the solvent is too volatile (having too high vapor pressure) the solvent may not remain in solution during heating. However, if the solvent is not volatile enough (too low vapor pressure) the solvent may be difficult to remove from the product or isolate from the alkoxy-functional organohydrogensiloxane oligomer.
  • the solvent may be an organic solvent.
  • the organic solvent can be an aromatic hydrocarbon such as benzene, toluene, or xylene, or a combination thereof.
  • Ingredient (D) may be one solvent. Alternatively, ingredient (D) may comprise two or more different solvents.
  • the amount of solvent can depend on various factors including the specific solvent selected and the amount and type of other ingredients selected for the mixture. However, the amount of solvent may range from 0 % to 99 %, or when present, 1 % to 99 %, and alternatively 2 % to 50 %, based on the weight of the mixture.
  • the method may optionally further comprise one or more additional steps.
  • the method may further comprise a step of: recovering a fraction containing the alkoxy- functional organohydrogensiloxane oligomer from the product.
  • the alkoxy- functional organohydrogensiloxane oligomer may comprise a ⁇ -adduct compound ⁇ i.e., where D is linear) and a corresponding a-adduct compound ⁇ i.e., where D is not linear) are difficult and/or costly to separate from one another, a fraction comprising both ⁇ - adduct compound and a-adduct compound may be recovered from the product after step 1 ) described above.
  • this fraction contain > 90% ⁇ -adduct compound, alternatively > 90% to 100% ⁇ -adduct compound, alternatively 92% to 100%, alternatively > 90% to ⁇ 100%, alternatively 92% to ⁇ 100%, and alternatively 95% to ⁇ 100% ⁇ -adduct compound, based on the combined amounts of ⁇ -adduct compound and a-adduct compound in the fraction.
  • Recovering this fraction may be performed by any convenient means, such as stripping or distillation, with heating or under vacuum, or a combination thereof.
  • the fraction described above comprising the ⁇ -adduct compound alkoxy- functional organohydrogensiloxane oligomer above is useful for functionalization of polyorganosiloxanes, including oligomers and longer chain polymers, containing aliphatically unsaturated functionality.
  • a hydrosilylation reaction of the SiH group in the alkoxy-functional organohydrogensiloxane oligomer of formula (X) with an aliphatically unsaturated group bonded to silicon in a polyorganosiloxane (such as a polydiorganosiloxane having aliphatically unsaturated terminal groups) can produce an alkoxy-functional polyorganosiloxane.
  • the polyorganosiloxane having aliphatically unsaturated terminal groups may have unit formula (XVII):
  • each R 7 is independently a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group, or a
  • each R ⁇ is independently an aliphatically unsaturated hydrocarbon group such as an alkenyl group exemplified by alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and alkynyl groups such as ethynyl and propynyl.
  • Subscript e is an integer of 0 or more
  • subscript f is an integer of 0 or more
  • subscript g is an integer of 0 or more
  • subscript h is an integer of 0 or more, with the proviso that a quantity (f + g) > 1 .
  • the polyorganosiloxane may be a polydiorganosiloxane.
  • the polydiorganosiloxane having aliphatically unsaturated terminal groups may have formula (XVIII):
  • R 7 2 R 8 SiO(R 7 2 SiO) d SiR 7 2 R 8 .
  • R 7 and R 8 are as described above.
  • Subscript d may be 0 or a positive number.
  • each R 7 may be an alkyl group or an aryl group as described above for R 1 .
  • subscript d has an average value of at least 2.
  • subscript d may have a value ranging from 2 to 2000.
  • the compound of formula (XVIII) may comprise a polydiorganosiloxane such as i) dimethylvinylsiloxy-terminated polydimethylsiloxane,
  • the alkoxy-functional polyorganosiloxane may be produced by combining the product or fraction including the ⁇ -adduct compound alkoxy-functional organohydrogensiloxane oligomer with a polydiorganosiloxane of formula (XVIII) as described above.
  • polyorganosiloxane may be performed by a method comprising:
  • hydrosilylation catalyst other than the rhodium diphosphine catalyst complex described above.
  • Suitable catalysts for catalyzing hydrosilylation reaction are known in the art and are commercially available.
  • Such hydrosilylation catalysts can be a platinum group metal, such as platinum.
  • the hydrosilylation catalyst may be a compound of such a metal, for example, chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core/shell type structure.
  • organopolysiloxanes include 1 ,3-diethenyl-1 ,1 ,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix.
  • Exemplary hydrosilylation catalysts are described in U.S. Patents 3,159,601 ; 3,220,972; 3,296,291 ; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,1 17; and 5,175,325 and EP 0 347 895 B.
  • Microencapsulated hydrosilylation catalysts and methods of preparing them are known in the art, as exemplified in U.S. Patents 4,766,176 and 5,017,654. Combining the starting materials may be performed at elevated temperature, such as heating at 50°C to 250°C.
  • polyalkoxy-functional polyorganosiloxanes produced by the hydrosilylation of described above may have formula:
  • > 90 mol% to 100 mol% of R 1 1 are ⁇ - adduct groups.
  • formula (XIX) 92% to ⁇ 100% % of R 1 1 are ⁇ -adduct groups.
  • the polyorganosiloxane having aliphatically unsaturated terminal groups is a polydiorganosiloxane of formula (XX):
  • poly-alkoxy functional polyorganosiloxane may have formula (XXI):
  • each is independently a divalent hydrocarbon group; where R ⁇ , R 2 , D and subscript c are as described above.
  • poly-alkoxy functional polyorganosiloxane may have formula
  • each D 1 is independently a divalent hydrocarbon group; where R 1 , R 2 , D and subscript c are as described above.
  • the poly-alkoxy functional polyorganosiloxanes, such as polyalkoxy-functional polydimethylsiloxanes, prepared as described above can be used in any application that utilizes reactivity of the alkoxy groups.
  • condensation reaction curable compositions such as sealant compositions.
  • Suitable condensation reaction curable compositions can be prepared by mixing starting materials comprising:
  • condensation reaction catalyst (ii) condensation reaction catalyst.
  • a condensation reaction curable composition including (i) the poly-alkoxy functional polyorganosiloxane will cure faster than a similar condensation reaction curable composition containing a different poly-alkoxy functional polyorganosiloxane (prepared using a conventional endblocker having higher branched isomer content).
  • Starting material (ii) is a condensation reaction catalyst.
  • Suitable condensation reaction catalysts include tin catalysts and titanium catalysts.
  • Suitable tin catalysts include organotin compounds where the valence of the tin is either +4 or +2, i.e., Tin (IV) compounds or Tin (II) compounds.
  • tin (IV) compounds include stannic salts of carboxylic acids such as dibutyl tin dilaurate, dimethyl tin dilaurate, di-(n-butyl)tin bis- ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide, carbomethoxyphenyl tin tris-uberate, dibutyl tin dioctanoate, dibutyl tin diformate, isobutyl tin triceroate, dimethyl tin dibutyrate, dimethyl tin di-neodeconoate, dibutyl tin di-neodeconoate, triethyl tin tartrate, dibutyl tin dibenzoate, butyltintri-2- ethylhexanoate, dio
  • Tin (IV) compounds are known in the art and are commercially available, such as Metatin® 740 and Fascat® 4202 from Acima Specialty Chemicals of Switzerland, Europe, which is a business unit of The Dow Chemical Company.
  • tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, stannous stearate, stannous naphthanate, stannous hexanoate, stannous succinate, stannous caprylate, and a combination thereof.
  • titanium catalysts include titanium esters such as tetra-n-butyltitanate tetraisopropyltitanate, tetra-2- ethylhexyltitanate, tetraphenyltitanate, triethanolamine titanate, organosiloxytitanium compounds, and dicarbonyl titanium compounds, such as titanium ethyl acetoacetate and bis(acetoacetonyl)-diisopropoxy titanium (IV).
  • a titanium catalyst may be used when the composition will be formulated as a room temperature vulcanizing sealant composition.
  • the amount of condensation reaction catalyst depends on various factors including the amount of starting material (i) and the types and amounts of any additional starting materials added to the composition, however the amount of condensation reaction catalyst may be 0.2 to 6, alternatively 0.5 to 3, parts by weight based on the weight of starting material (i).
  • the condensation reaction curable composition may further comprise one or more additional ingredients distinct from ingredients (i) and (ii). Suitable additional ingredients are exemplified by (iii) a filler; (iv) a filler treating agent; (v) a crosslinker; (vi) a surface modifier, (vii) a drying agent; (viii) an extender, a plasticizer, or a combination thereof; (ix) a biocide; (x) a flame retardant; (xi) a chain lengthener; (xii) an endblocker; (xiii) a nonreactive binder; (xiv) an anti-aging additive; (xv) a water release agent; (xvi) a pigment; (xvii) a rheological additive; (xviii) a vehicle (such as a solvent and/or a diluent); (xix) a tackifying agent; (xx) a corrosion inhibitor; and a combination of two or more thereof.
  • Starting material (iii) that may be added to the composition is a filler.
  • the filler may comprise a reinforcing filler, an extending filler, or a combination thereof.
  • the composition may optionally further comprise ingredient (iii-1 ), a reinforcing filler, which when present may be added in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, based on the weight of the composition.
  • the exact amount of starting material (iii-1 ) depends on various factors including the form of the reaction product of the composition and whether any other fillers are added.
  • suitable reinforcing fillers include precipitated calcium carbonates and reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica.
  • Suitable precipitated calcium carbonates include Winnofil® SPM from Solvay and Ultrapflex® and Ultrapflex® 100 from Specialty Minerals, Inc. Fumed silicas are known in the art and commercially available; e.g., fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.
  • the composition may optionally further comprise starting material (iii-2) an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition.
  • extending fillers include crushed quartz, aluminum oxide, magnesium oxide, ground calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof.
  • Extending fillers are known in the art and commercially available; such as a ground quartz sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV.
  • Examples of extending calcium carbonates include CS-1 1 from Imerys, G3T from Huber, and Omyacarb 2T from Omya.
  • the composition may optionally further comprise starting material (iv) a treating agent.
  • the amount of starting material (iv) can vary depending on factors such as the type of treating agent selected and the type and amount of particulates to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ. However, starting material (iv) may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of the composition.
  • Particulates, such as the filler, the physical drying agent, certain flame retardants, certain pigments, and/or certain water release agents, when present, may optionally be surface treated with starting material (iv).
  • Particulates may be treated with starting material (iv) before being added to the composition, or in situ.
  • Starting material (iv) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid.
  • fatty acids include stearates such as calcium stearate.
  • organosilicon filler treating agents that can be used as starting material (iv) include compositions normally used to treat silica fillers such as organochlorosilanes, organosiloxanes, organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanes such as C6H-
  • treating agents include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and
  • starting material (iv) may comprise an alkoxysilane having the formula (XXIII): R 1 3pSi(OR 1 4 )(4_p), where subscript p may have a value ranging from 1 to 3, alternatively subscript p is 3.
  • Each R 1 3 j S independently a monovalent organic group, such as a monovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to 30 carbon atoms, alternatively 8 to 18 carbon atoms.
  • R 1 3 is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; and aromatic groups such as benzyl and phenylethyl.
  • R 1 3 ma y be saturated or unsaturated, and branched or unbranched. Alternatively, R 1 3 may be saturated and unbranched.
  • Each R 1 4 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • Starting material (iv) is exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane,
  • dodecyltrimethoxysilane dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.
  • Alkoxy-functional oligosiloxanes may also be used as treating agents.
  • suitable alkoxy-functional oligosiloxanes include those of the formula (XXIV):
  • each R 1 5 may be an alkyl group.
  • Each R 1 6 may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms.
  • Each R 1 7 may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.
  • a polyorganosiloxane capable of hydrogen bonding is useful as a treating agent.
  • This strategy to treating surface of a filler takes advantage of multiple hydrogen bonds, either clustered or dispersed or both, as the means to tether the compatibilization moiety to the filler surface.
  • the polyorganosiloxane capable of hydrogen bonding has an average, per molecule, of at least one silicon-bonded group capable of hydrogen bonding.
  • the group may be selected from: an organic group having multiple hydroxyl functionalities or an organic group having at least one amino functional group.
  • the polyorganosiloxane capable of hydrogen bonding means that hydrogen bonding is the primary mode of attachment for the polyorganosiloxane to a filler.
  • the polyorganosiloxane may be incapable of forming covalent bonds with the filler.
  • the polyorganosiloxane may be free of condensable silyl groups e.g., silicon bonded alkoxy groups, silazanes, and silanols.
  • the polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide-siloxane polymer, an amino-functional polyorganosiloxane, and a combination thereof. Alternatively, the polyorganosiloxane capable of hydrogen bonding may be a saccharide-siloxane polymer.
  • Starting material (v) is a crosslinker.
  • Starting material (v) may comprise a silane crosslinker having hydrolyzable groups or partial or full hydrolysis products thereof.
  • Starting material (v) has an average, per molecule, of greater than two substituents reactive with the alkoxy groups on starting material (i).
  • Examples of suitable silane crosslinkers for starting material (v) may have general formula (XXV):
  • each R 1 0 is independently a monovalent hydrocarbon group such as an alkyl group; each R ⁇ is a hydrolyzable substituent, for example, a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group; and each instance of subscript k may be 0, 1 , 2, or 3. For starting material (v), subscript k has an average value greater than 2.
  • subscript k may have a value ranging from 3 to 4.
  • each R9 may be independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime.
  • starting material (v) may be selected from an acyloxysilane, an
  • alkoxysilane a ketoximosilane, and an oximosilane.
  • Starting material (v) may comprise an alkoxysilane exemplified by a
  • dialkoxysilane such as a dialkyldialkoxysilane
  • a trialkoxysilane such as an
  • alkyltrialkoxysilane a tetraalkoxysilane; or partial or full hydrolysis products thereof, or another combination thereof.
  • suitable trialkoxysilanes include
  • ethyltriethoxysilane isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane.
  • tetraalkoxysilanes include tetraethoxysilane.
  • the amount of the alkoxysilane that is used in the composition may range from 0.5 to 15, parts by weight per 100 parts by weight of starting material (i).
  • Starting material (v) may comprise an acyloxysilane, such as an acetoxysilane.
  • Acetoxysilanes include a tetraacetoxysilane, an organotriacetoxysilane, a
  • the acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyi groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3- trifluoropropyl.
  • Exemplary acetoxysilanes include, but are not limited to,
  • tetraacetoxysilane methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane,
  • octyltriacetoxysilane dimethyldiacetoxysilane, phenylmethyldiacetoxysilane,
  • starting material (v) may comprise
  • organotriacetoxysilanes for example mixtures comprising methyltriacetoxysilane and ethyltriacetoxysilane.
  • the amount of the acetoxysilane that is used in the curable silicone composition may range from 0.5 to 15 parts by weight per 100 parts by weight of starting material (i); alternatively 3 to 10 parts by weight of acetoxysilane per 100 parts by weight of starting material (i).
  • silanes suitable for starting material (v) containing both alkoxy and acetoxy groups that may be used in the composition include
  • Aminofunctional alkoxysilanes suitable for starting material (v) are exemplified by H 2 N(CH 2 )2Si(OCH3)3, H 2 N(CH2)2Si(OCH 2 CH3)3, H 2 N(CH 2 )3Si(OCH3)3,
  • Suitable oximosilanes for starting material (v) include alkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanes such as methoxytrioximosilane, ethoxytrioximosilane, and propoxytrioximosilane; or alkenyltrioximosilanes such as propenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanes such as
  • vinyloximosilane alkenylalkyldioximosilanes such as vinyl methyl dioximosilane, vinyl ethyldioximosilane, vinyl methyldioximosilane, or vinylethyldioximosilane; or
  • Suitable ketoximosilanes for starting material (v) include methyl
  • ethoxytri(ethylmethylketoxime)silane methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.
  • starting material (v) may be polymeric.
  • starting material (v) may comprise a disilane such as bis(triethoxysilyl)hexane), 1 ,4- bis[trimethoxysilyl(ethyl)]benzene, and bis[3-(triethoxysilyl)propyl] tetrasulfide.
  • Starting material (v) can be one single crosslinker or a combination comprising two or more crosslinkers that differ in at least one of the following properties:
  • Starting material (vi) is an adhesion promoter.
  • Suitable adhesion promoters for starting material (vi) may comprise a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane, an aminofunctional silane, a mercaptofunctional silane, or a combination thereof.
  • Adhesion promoters are known in the art and may comprise silanes having the formula (XXVI):
  • each R24 is independently a monovalent organic group having at least 3 carbon atoms;
  • R 2 ⁇ contains at least one SiC bonded substituent having an adhesion-promoting group, such as amino, epoxy, mercapto or acrylate groups;
  • subscript t has a value ranging from 0 to 2;
  • subscript u is either 1 or 2; and the sum of (t + u) is not greater than 3.
  • the adhesion promoter may comprise a partial condensate of the above silane.
  • the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional compound.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional alkoxysilane.
  • the functional alkoxysilane can have the formula
  • Each R2 is independently a monovalent organic group with the proviso that at least one
  • R 27 is an unsaturated organic group or an epoxy-functional organic group.
  • Epoxy- functional organic groups for R 27 are exemplified by 3-glycidoxypropyl and
  • R 27 (epoxycyclohexyl)ethyl.
  • Unsaturated organic groups for R 27 are exemplified by 3- methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl.
  • Each R 28 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • R 2 ⁇ is exemplified by methyl, ethyl, propyl, and butyl.
  • Examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
  • suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.
  • the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, as described above, or a physical blend of the hydroxy- terminated polyorganosiloxane with the epoxy-functional alkoxysilane.
  • the adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane.
  • the adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and a reaction product of hydroxy- terminated methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl/dimet ylsiloxane copolymer.
  • the adhesion promoter may comprise an aminofunctional silane, such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3, H 2 N(CH2)2Si(OCH 2 CH3)3, H 2 N(CH 2 )3Si(OCH3)3, H 2 N(CH2)3Si(OCH 2 CH3)3, CH 3 NH(CH2)3Si(OCH 3 )3, CH 3 NH(CH2)3Si(OCH 2 CH3)3, CH 3 NH(CH2)5Si(OCH 3 )3, CH 3 NH(CH2)5Si(OCH2CH 3 )3, H 2 N(CH2)2 H(CH2)3Si(OCH 3 )3,
  • an aminofunctional silane such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3, H 2 N(CH2)2Si(OCH 2 CH3)3, H 2 N(CH 2 )3Si(OCH3)3,
  • the adhesion promoter may comprise a mercaptofunctional alkoxysilane, such as 3-mercaptopropyltrimethoxysilane or 3- mercaptopropyltriethoxysilane.
  • starting material (vi) depends on various factors including the type of adhesion promoter selected and the end use of the composition and its reaction product. However, starting material (vi), when present, may be added to the composition in an amount ranging from 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts. Starting material (vi) may be one adhesion promoter. Alternatively, starting material (vi) may comprise two or more different adhesion promoters that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • ingredients for the condensation reaction curable composition described above there may be overlap between types of starting materials because certain starting materials described herein may have more than one function.
  • certain alkoxysilanes may be useful as filler treating agents, as adhesion promoters, and as crosslinkers.
  • the crosslinker, the filler, and the adhesion promoter may each be present in the composition.
  • the crosslinker may comprise an alkyl trialkoxysilane, such as methyltrimethoxysilane;
  • the filler may comprise an extending filler such as calcium carbonate;
  • the adhesion promoter may comprise an alkoxysilane other than the crosslinker, such as N-(3-
  • composition described above may be prepared as a one part composition, for example, by combining all ingredients by any convenient means, such as mixing.
  • a one-part composition may be made by optionally combining (e.g., premixing) (i) the alkoxy-functional polyorganosiloxane with all or part of (iii) the filler, when present; and mixing this with a pre-mix comprising the catalyst (ii) and, when present (v) the crosslinker.
  • Other additives such as an anti-aging additive and a pigment may be added to the mixture at any desired stage.
  • a final mixing step may be performed under substantially anhydrous conditions, and the resulting compositions are generally stored under substantially anhydrous conditions, for example in sealed containers, until ready for use.
  • the composition may be prepared as a multiple part ⁇ e.g., 2 part) composition when a crosslinker is present.
  • the catalyst and crosslinker are stored in separate parts, and the parts are combined shortly before use of the composition.
  • a two part curable composition may be prepared by combining ingredients comprising the alkoxy-functional polyorganosiloxane and the crosslinker to form a first (curing agent) part by any convenient means such as mixing.
  • a second (base) part may be prepared by combining starting materials comprising a catalyst and the alkoxy-functional polyorganosiloxane by any convenient means such as mixing.
  • the starting materials may be combined at ambient or elevated temperature and under ambient or anhydrous conditions, depending on various factors including whether a one part or multiple part composition is selected.
  • the base part and curing agent part may be combined by any convenient means, such as mixing, shortly before use.
  • the base part and curing agent part may be combined in relative amounts of base: curing agent ranging from 1 :1 to 10:1 .
  • the equipment used for mixing the starting materials is not specifically restricted. Examples of suitable mixing equipment may be selected depending on the type and amount of each ingredient selected. For example, agitated batch kettles may be used for relatively low viscosity compositions, such as compositions that would react to form gums or gels. Alternatively, continuous compounding equipment, e.g., extruders such as twin screw extruders, may be used for more viscous compositions and compositions containing relatively high amounts of particulates. Exemplary methods that can be used to prepare the compositions described herein include those disclosed in, for example, U.S. Patent Publications US 2009/0291238 and US 2008/0300358.
  • compositions made as described above may be stable when the stored in containers that protect the compositions from exposure to moisture, but these compositions may react via condensation reaction when exposed to atmospheric moisture.
  • Yield means molar amount alkoxy-functional organohydrogensiloxane oligomer produced / molar amount alkoxy-functional organohydrogensiloxane oligomer possible based on the amount of limiting reagent (the aliphatically unsaturated alkoxysilane).
  • Selectivity means the ratio of linear isomer/branched isomer of the alkoxy-functional organohydrogensiloxane (where isomers have the same molecular weight).
  • a 250 mL round bottom flask containing a stirbar was loaded with 80 g of TMDS, and to it was affixed an addition funnel containing 82.77 g of VTMS.
  • the apparatus was thoroughly purged with nitrogen and then pre-heated to 50 °C.
  • a steady addition of the VTMS was initiated ( ⁇ 1 drop/sec) and then 2.38 mL of a 0.005 M solution of [Rh(dppe)CI]2 in THF was added.
  • the addition was continued at such a rate that the reaction mixture temperature did not exceed 70 °C after the first 50% of VTMS was added, and then 80 °C for the second half of the addition. Following the addition, the reaction mixture was allowed to react for 16 h at 80 °C.
  • the reaction mixture was then purified by vacuum distillation, which resulted in a light fraction (solvents, unreacted reagents, and light byproducts), a desired product fraction (approximately distilling at 1 .25 Torr (0.1666 kPa) and 55-60 °C), and a heavy fraction which was left behind in the distillation flask.
  • the yield of the desired product fractions was 103.8 g (65% yield), and this fraction contained -96% of the linear isomer and 4% of the branched isomers.
  • the yield of the minor byproducts varied, and sometimes contained additional species such as the dehydrogenative silylation product, however the linear isomer was always the major product in >90% yield.
  • a solution of 1 % Pt catalyst in toluene was prepared.
  • VTM in an amount of 18.05 g was added at a rate of 275 ⁇ to a flask containing 1 1 .97 g M'D'M' in at a temperature of 40 °C under N2 with rapid stirring while cooling the flask, by means of a syringe pump.
  • 5% of the total VTM was initially added, followed by 1 0 pm Pt catalyst (39 ⁇ _ of the 1 % solution Pt in toluene) to start the exotherm, and then the addition of the remaining VTM was begun.
  • the temperature was monitored by a thermocouple and kept below 80 °C by controlling the addition rate.
  • the reaction solution was stirred at 75°C for 0.5 h, allowed to cool, and characterized by GC which showed the product mixture contained 10% monofunctional oligomer, 68% difunctional oligomer, and 20% trifunctional oligomer.
  • the sample was purified by distillation under 1 Torr (0.1333kPa) to give 1 6.9 g M'D'M' EHM (yield: 56%) with a boiling point of 135-1 37°C at 1 Torr (0.1333kPa).
  • the sample was characterized by GC,
  • a rhodium diphosphine catalyst, [Rh 1 ,2-bis(diphenylphosphino)ethane Cl]2 was dissolved in THF to prepare a 1 millimolar (mM) catalyst solution.
  • mM millimolar
  • a three-neck round bottom flask fitted with a thermocouple and a cold water condenser was charged with 9.96 g M'D'M' and 1 5.04 g VTM.
  • the flask was purged with N2, and the mixture in the flask was heated to 80°C, followed by the addition of [Rh(dppe)CI]2 solution (1 mL). A slight exotherm was observed, with the temperature elevated to 96 °C within 5 minutes of addition.
  • this oligomer was composed of 98% M'D'M' EHM (shown below) and 2% dehydrogenative species.
  • the M'D'M' EHM comprised 97% ⁇ isomer and 3% a isomer, as well as 53% D-H isomer (top product structure) and 47% M-H isomer (bottom product structure, shown in the reaction scheme above).
  • Example 4 The procedure of Example 4 was repeated, except that M'T Pr (1 5.0 g), VTM (1 5.0 g), and platinum catalyst solution in toluene (39 ⁇ _) were used as starting materials.
  • the crude product contained 14% monofunctional oligomer, 54% difunctional oligomer, and 31 % trifunctional oligomer by GC (FID).
  • the sample was purified by distillation under 1 Torr (0.1333kPa) to give 1 3.5 g pure Pr-T EHM (yield: 45%). This was characterized by
  • Example 7 [0082] The procedure of example 5 was repeated, except that MT Pr (29.7 g), VTM (29.7 g), and [Rh(dppe)CI]2 (4 mM in THF, 0.5 ml_, 2 ⁇ ) were used as starting materials. The reaction was conducted at 80 °C for 7 h. The crude product contained 18% monofunctional oligomer, 63% difunctional oligomer, and 1 8% trifunctional oligomer by GC (FID). The sample was purified by distillation under 1 Torr (0.1333kPa) to give 25.8 g pure difunctional Pr-T EHM (yield: 44%). The Pr-T EHM was characterized by GC (retention time: 30.5,
  • hydrosilylation product fraction was entirely composed of
  • HSiMe20SiMe2H (25 mmol) was added to a 20 mL glass vial containing a stirbar and to the mixture was added 123 ⁇ of 0.005 M [Rh(dppe)CI]2 (0.01 M in Rh) in THF. The mixture was stirred at 70°C for 16 h. The reaction mixture was then analyzed by GC-MS and GC-FID, which indicated that a reaction was partially complete and that the ratio of linear to branched to other unidentified isomers was 98.5 : 1 .0 : 0.5.
  • HSiMe20SiMe2H (20 mmol) was added to a 20 mL glass vial containing a stirbar and to the mixture was added 98 ⁇ of 0.005 M [Rh(dppe)CI]2 (0.01 M in Rh) in THF. The mixture was stirred at 70°C for 16h. The reaction mixture was then analyzed by GC-MS and GC-FID, which indicated that a reaction was partially complete and that the ratio of the linear hydrosilylation product to other isomers was 99.5 : 0.5.
  • Example 1 [0089] To a mixture of 5.00 g of HSiMe2(OSiMe2) x OSiMe2H (-6.8 mmol of Si-H) and
  • trimethoxy-functional polydimethylsiloxane prepared by hydrosilylation reaction of an ethyltrimethoxysilyl- terminated tetramethyldisiloxane and an ⁇ , ⁇ -vinyl-terminated polydimethylsiloxane.
  • a mixture of i) methyltrimethoxysilane, ii) tetra-n-butoxy titanate, iii) 3- mercaptopropyltrimethoxysilane, iv) mixture of 80% titanium ethyl acetoacetate and 20% methyltrimethoxysilane, and v) N-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratio equivalent to the ratio shown in a table below. From this mixture, 13.16g was added to the speed mixer cup. The cup was mixed in a DAC 600.2 VAC-P Speedmixer for 30 seconds at 800 revolutions per minute (rpm), then 30 seconds at 1500 rpm.
  • the cup was de-aired by mixing 30 seconds at 800 rpm and 5 pounds per square inch (psi) (34.5kPa), 30 seconds at 1500 rpm and 5 psi (34.5kPa), and 30 seconds at 800 rpm and 14.7 psi (101 .35kPa).
  • the resulting sealant composition was transferred to Semco® tubes via a hand operated cup press. it ) mparav ( at Starting Materials Amount (g)
  • a mixture of i) methyltrimethoxysilane, ii) tetra-n-butoxy titanate, iii) 3-mercaptopropyltrimethoxysilane, iv) mixture of 80% titanium ethyl acetoacetate and 20% methyltrimethoxysilane, and v) N-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratio equivalent to the ratio shown in the tables below. From this mixture, 56.15g was added to the pot. The pot was fitted to the mixer, and was voided of air via vacuum pump and filled with N2 three times to create an inert atmosphere. The pot was mixed five minutes at 50 rpm.
  • a mixture of i) methyltrimethoxysilane, ii) mixture of 80% titanium ethyl acetoacetate and 20% methyltrimethoxysilane, iii) tetra-n-butoxy titanate, iv) 3- mercaptopropyltrimethoxysilane, and v) N-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratio equivalent to the ratio seen in the above formulations. To the cup was added 21 .05g of this mixture. The cup was then mixed in a DAC 600.2 VAC-P Speedmixer one minute at 2000rpm.
  • trimethoxy-functional polydimethylsiloxane prepared by hydrosilylation reaction of an ethyltrimethoxysilyl-terminated tetramethyldisiloxane and an ⁇ , ⁇ -vinyl-terminated polydimethylsiloxane.
  • a mixture of i) methyltrimethoxysilane, ii) mixture of 80% titanium ethyl acetoacetate and 20% methyltrimethoxysilane, iii) tetra-n-butoxy titanate, iv) 3- mercaptopropyltrimethoxysilane, and v) N-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratio equivalent to the ratio seen in the above formulations. From this mixture, 84.20g was added to the pot. The pot was fitted to the mixer, and was voided of air via vacuum pump and filled with N2 three times to create an inert atmosphere. The pot was mixed five minutes at 50 rpm.
  • composition samples prepared as described above were evaluated using the following test methods.
  • a 100 mil slab of sealant was drawn down on a piece of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • a small strip of PET is then lightly pressed onto the surface of the sealant to check for cure. When no sealant is transferred to the strip of PET, the sealant is considered tack free.
  • the tack-free time is faster with the sealant composition containing the polydimethylsiloxane with the higher content ( ⁇ 95%) of the beta adduct when compared to a sealant composition containing the same starting materials except for a polydimethylsiloxane with a mixture of 70% ⁇ 30% ⁇ isomers of the ethyltrimethoxysilyl group.
  • the skin over time was faster, where samples 7 and 8 have the same skin over time. All samples were tested side by side to eliminate the temperature and humidity variable on cure.
  • hydrosilylation product fraction was entirely composed of
  • HSiMe20SiMe2H (25 mmol) was added to a 20 mL glass vial containing a stirbar and to the mixture was added 123 ⁇ of 0.005 M [Rh(dppe)CI] 2 (0.01 M in Rh) in THF. The mixture was stirred at 70°C for 16 h. The reaction mixture was then analyzed by GC-MS and GC-FID, which indicated that a reaction was partially complete and that the ratio of linear to branched to other unidentified isomers was 98.5 : 1 .0 : 0.5.
  • HSiMe20SiMe2H (20 mmol) was added to a 20 mL glass vial containing a stirbar and to the mixture was added 98 ⁇ of 0.005 M [Rh(dppe)CI] 2 (0.01 M in Rh) in THF. The mixture was stirred at 70°C for 16h. The reaction mixture was then analyzed by GC-MS and GC-FID, which indicated that a reaction was partially complete and that the ratio of the linear hydrosilylation product to other isomers was 99.5 : 0.5. [0106] The overall yields are shown below in Table 17.
  • the cup was fitted with a cap that contained a hole as to allow the contents of the cup to be exposed to a vacuum environment.
  • the cup was de-aired by mixing 30 seconds at 800 rpm and 5 psi (34.5kPa), 30 seconds at 1500 rpm and 5 psi (34.5kPa), and 30 seconds at 800 rpm and 14.7 psi (101 .35kPa).
  • the resulting sealant was transferred to Semco® tubes via a hand operated cup press. A reasonable variance was allowed when adding starting materials.
  • polyorganosiloxane is endblocked with an alkoxy-functional organohydrogensiloxane oligomer prepared by the method described herein and having > 90 mol% of linear divalent hydrocarbon linking groups, and the resulting endblocked polyorganosiloxane is formulated into a condensation reaction curable composition, the composition cures faster than a comparative composition containing a polyorganosiloxane endblocked with an alkoxy-functional organohydrogensiloxane oligomer having a lower amount of linear divalent hydrocarbyl linking groups and a higher amount of branched divalent hydrocarbon linking groups.

Abstract

L'invention concerne un procédé de préparation d'un produit qui consiste à combiner des matières premières comprenant A) un oligomère de siloxane comportant des atomes d'hydrogène liés au silicium, B) un alcoxysilane comportant au moins un groupe aliphatiquement insaturé apte à subir une réaction d'hydrosilylation et C) un catalyseur à complexe de dirhodium. Le procédé peut être utilisé pour produire un composé de formule (formule (F)). Ce composé peut être utilisé dans une réaction d'hydrosilylation avec un polyorganosiloxane à fonction vinyle. Le produit ainsi obtenu comprend un polyorganosiloxane à fonction éthyltriméthoxysilyle utile dans des compositions de produits de scellement durcissables par une réaction de condensation.
PCT/US2018/039377 2017-06-26 2018-06-26 Procédé d'hydrosilylation d'alcoxysilanes aliphatiquement insaturés et d'oligomères d'organosiloxane à terminaison hydrogène pour préparer des polymères à terminaison alcoxysilyle utiles pour fonctionnaliser des polyorganosiloxanes à l'aide d'un catalyseur au rhodium WO2019005710A1 (fr)

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JP2019567993A JP7189157B2 (ja) 2017-06-26 2018-06-26 脂肪族不飽和アルコキシシラン及び水素末端オルガノシロキサンオリゴマーをヒドロシリル化して、ロジウム触媒を使用してポリオルガノシロキサンを官能化するのに有用なアルコキシシリル末端ポリマーを調製する方法
US16/617,679 US11098163B2 (en) 2017-06-26 2018-06-26 Method for hydrosilylation of aliphatically unsaturated alkoxysilanes and hydrogen terminated organosiloxane oligomers to prepare alkoxysilyl terminated polymers useful for functionalizing polyorganosiloxanes using a rhodium catalyst
CN201880038458.2A CN110770280B (zh) 2017-06-26 2018-06-26 用于制备烷氧基官能有机氢硅氧烷低聚物的方法
EP18743152.3A EP3645606A1 (fr) 2017-06-26 2018-06-26 Procédé d'hydrosilylation d'alcoxysilanes aliphatiquement insaturés et d'oligomères d'organosiloxane à terminaison hydrogène pour préparer des polymères à terminaison alcoxysilyle utiles pour fonctionnaliser des polyorganosiloxanes à l'aide d'un catalyseur au rhodium

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CN112789283A (zh) * 2019-09-11 2021-05-11 美国陶氏有机硅公司 用于制备烷氧基官能有机氢硅氧烷低聚物的方法和所述低聚物的用途

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CN112789283A (zh) * 2019-09-11 2021-05-11 美国陶氏有机硅公司 用于制备烷氧基官能有机氢硅氧烷低聚物的方法和所述低聚物的用途
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CN112789283B (zh) * 2019-09-11 2022-07-26 美国陶氏有机硅公司 用于制备烷氧基官能有机氢硅氧烷低聚物的方法和所述低聚物的用途

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